FI92642C - Antimicrobial composition - Google Patents

Description

92642

Antimicrobial composition

This invention relates to compositions having anti-microbial properties. Such compositions have 5 uses as industrial biocides.

Industrial biocides are antimicrobial agents which have an antibacterial, antifungal and / or antifouling effect and are therefore useful in preventing or reducing industrial pollution by various microbial species such as bacteria, fungi and / or algae. Agents of this type can be used to protect substrates that are sensitive to the growth of microorganisms. Thus, depending on its individual properties, the industrial biocide can be used, for example, in the preservation of paints, latexes, adhesives, leather, wood, metal fillers and cooling water.

Many compounds with antimicrobial properties are commercially available and can be used as industrial biocides. Iodine-containing compounds with antifungal properties are available. Compounds with antifungal properties can be added to paints to provide improved resistance to fungal growth on the paint film. However, iodine-containing compounds are generally sensitive to discoloration upon exposure to light, and therefore many iodine-containing compounds are not suitable for use as paint film fungicides. In addition, useful biocides are effective against a wide variety of microbial species, and an action against a broad spectrum of fungi, along with anti-algal properties, is particularly desirable. Such properties are seldom achievable with a single substance. The use of biocidal mixtures has been proposed, but it appears that such mixtures have not been entirely satisfactory. Thus, substances with a useful property ratio are increasingly sought.

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We have now found biocide mixtures with a particularly useful property ratio that can be started with other biocide combinations.

According to this invention there is provided a composition comprising (a) at least one halogenated aromatic 1,2- or 1,3-dinitrile, (b) at least one substituted urea and (c) at least one halogenated aromatic alkyl sulfoxide, or - a sulfone in which, when the aromatic group is the only halogen -10 va group, it contains at least four halogen substituents.

In component (a), two nitrile groups are located in the aromatic ring in the 1,2- or 1,3-position relative to each other. Thus component (a) may be phthalonitrile or isophthalonitrile. Substances suitable for use as component (a) have the general formula:

CN

2 ° - (^ j) -C "wherein each X, which may be the same or different, is a halogen atom, n is from one to four and the nitrile groups are in either the 1,2- or 1,3-position relative to each other.

When n is less than four, the atoms in the aromatic ring are hydrogen atoms. We have obtained useful results when n is four. Each X group is preferably a chlorine or fluorine atom. Usually all X groups are the same. Compounds that can be used as component (a) of the composition of this invention 35 are disclosed in U.S. Patent Nos. 3,290,353 and 3,331,735 3. As described in more detail in U.S. Patent No. 3,290,353, compounds that can be used as component (a), can be prepared by reacting the corresponding acid halide, especially the acid chloride, with ammonia to give the corresponding amide, which is then reacted with a dehydrating agent such as phosphorus pentoxide. The process described above is suitable for the preparation of chlorinated aromatic dinitrile from which a fluorinated analog can be prepared by a halogen exchange reaction.

Compounds that can be used as component (a) of the composition of the present invention include tetrachloroisophthalonitrile and tetrafluoroisophthalonitrile.

Compositions with beneficial properties have been prepared in which component (a) is tetrachloroiso-phthalonitrile.

Component (b) of the composition of this invention contains at least one substituted urea. Substituted urea typically contains at least one substituent on each nitrogen atom. One class of urea compounds that may be used contains one substituent group which is or contains an aromatic group ("aromatic substituent"), and there is no other substituent attached to the nitrogen atom to which the aromatic substituent is attached. One or two substituents may be attached to the second nitrogen atom, and these substituents are typically alkyl, alkenyl, alkynyl, alkoxy or cycloalkyl groups. Substituted ureas that can be used as component (b) typically have the formula:

Ar 0 λ} - i - H ^ ^ R2 35 4 92642 where

Ar is aryl, substituted aryl, heterocyclic or substituted heterocyclic, R 1 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, cycloalkyl, substituted cycloalkyl, alkoxy- or a substituted alkoxy group and R 2 is a hydrogen atom or a group defined for R 1.

Substituted groups may contain one or more substituents which may be a hydrocarbon group, a halogen atom, a hydrocarbonoxy group, a hydroxyl group and an alkylaminosulfonyl group, or a combination of such substituents.

The group Ar may be an unsubstituted aryl group such as a phenyl group, but may contain at least one substituent which is a halogen atom, an alkyl group, an alkoxy group or an aryloxy group which may itself be substituted. The group Ar can be, for example, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-isopropylphenyl-20-, 3-chloro-4-bromophenyl, 3-chloro-4-methylphenyl, 4- ( 4'-chlorophenoxy) phenyl or 4- (4'-methoxyphenoxy) phenyl. If the group Ar is or contains a heterocyclic group, it may be, for example, a benzothiazol-2-yl group or it may be a heterocyclic group having aromatic features such as a pyridyl group.

The groups R1 and R2 are typically unsubstituted. In general, R1 and R2 each contain up to six carbon atoms, in particular up to four carbon atoms. If R2 is other than a hydrogen atom, the groups R1 and R2 may be the same or different. Typically R 2 is a hydrogen atom or a methyl group. The group R1 may be, for example, a methyl, n-butyl, methoxy, 2-methylcyclohexyl or 3-butynyl group.

The Ar group is preferably unsubstituted or particularly preferably substituted by one or two substituents which are lower alkyl groups than halogen atoms, i.e. alkyl groups containing up to six carbon atoms and in particular up to four and carbon atoms. It is particularly preferred that in the compounds containing the preferred Ar group, the groups R1 and R2 are hydrogen, methyl and methoxy groups and at least one of R1 and R2 is other than hydrogen. Most preferred are compounds wherein R 1 and R 2 are both methyl groups.

Substituted ureas that can be used as component (b) include 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3-chloro-4-bromophenyl) -1-methyl-1-methoxyurea , 3- (4-isopropylphenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methyl-1-methoxyurea, 3- (3-chloro-4-methylphenyl) -1,1- dimethylurea, 1,1-dimethyl-3-phenylurea, 3- (4-chlorophenyl) -1,1-dimethylurea and 3- (3-chloro-4-methoxyphenyl) -1,1-dimethylurea.

Other substituted ureas include 1,1-dimethyl-3- (3-trifluoromethylphenyl) urea, 3- (3-t-butylcarbamoyloxy) phenyl-1,1-dimethylurea, 1,1-dimethyl-3- (4-trifluoromethylphenyl) urea, 3- [3-chloro-4- (chlorodifluoromethylthio) phenyl] -1,1-di-methylurea, 3- (3- [1 ', 1', 2 ', 2'-tetrafluoroethoxy] phenyl) -1,1-dimethylurea , 3- (3-chloro-4-trifluoromethoxyphenyl) -1,1-dimethylurea, 3- [4- (4'-chlorophenoxy) phenyl] -1,1-dimethylurea, 3- [4- (4'-methoxyphenoxy) ) phenyl] -1,1-dimethylurea, 3- (4-chlorophenyl) -1-methyl-1- (3-butynyl) urea, 3- (3,4-dichlorophenyl) -1-methyl-n-butylurea, 3 -phenyl-1- (2-methylcyclohexyl) urea and 3- (benzothiazol-2-yl) -1-methylurea.

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Compositions with useful properties have been prepared in which component (b) is 3- (3,4-dichlorophenyl) -1,1-dimethylurea.

Substituted ureas which can be used as component (b) can be prepared by known methods, for example as described in GB Patents 691403 and 692589 and U.S. Patents 2655455 and 2768971.

Substances suitable for use as component (c) have the general formula:

Ar 1 SOX R 3 wherein Ar 1 is aryl, substituted aryl, heterocyclic or substituted heterocyclic, R 3 is alkyl or substituted alkyl, x is one or two and at least one of Ar 1 and R 3 contains at least one halogen substituent and, if R3 does not contain halogen, so Ar1 contains at least four halogen substituents.

Substituents which may be present in Ar1 and R3 include at least one halogen atom, a hydrocarbon group or a hydrocarbonoxy group. Arx or R3, or both, contain at least one halogen atom substituent.

In one class of compounds which can be used as component (c), Ar 1 is a heterocyclic group, in particular a substituted heterocyclic group having aromatic properties, such as a pyridine ring containing at least one halogen substituent, in particular at least two halogen atoms, for example three halogens . In such a compound, R 3 is preferably an unsubstituted alkyl group containing 1 to 12 carbon atoms, and Ar 1 preferably contains at least four halogen substituents. Compounds of this type and the preparation of such compounds are described in more detail in GB Patent 1,103,606 and U.S. Patent Nos. 3,296,272 and 3,371,011. As described in more detail in the aforementioned patents, compounds of this type can be prepared by oxidizing the corresponding thiol. Suitable compounds of this type are those in which Ar1 is a pyridine ring having four halogen substituents, R3 is an unsubstituted lower alkyl group, i.e. an alkyl group containing up to six carbon atoms, and x is two. Compounds of this type include 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and 2,3,5,6-tetrachloro-4- (iosopropylsulfonyl) pyridine.

In another class of compounds that can be used as component (c), Ar1 contains an aryl group, R3 is a halogen-substituted methyl group and x is two. Compounds of the general type of Tamdn and their preparation are described in more detail in U.S. Patent Nos. 3,632,859 and 3,663,623. As described in U.S. Patent No. 3,632,859, compounds of this type can be prepared by halogenating sulfonylacetic acid, for example, sodium hydroxide in sodium hydride iodide. Method 25 of U.S. Patent No. 3,663,623 differs in that the halogenation step is performed using iodine monochloride in a substantially neutral solution. Suitable compounds of this type are those in which Ar1 is an alkyl-substituted aryl group such as 4-methylphenyl and R3 is a diiodomethyl group.

Compositions having useful properties have been prepared in which component (c) is 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine or diiodomethyl-4-methylphenylsulfone.

In a particular embodiment of this invention, there is provided a composition comprising (a) tetrachloro-8,92642 isophthalonitrile, (b) 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and (c) 2,3, 5,6-tetrachloro-4- (methylsulfonyl) pyridine or diiodomethyl-4-methylphenylsulfone.

The amount of each component in the composition is preferably at least 10% by weight of the total weight of components (a), (b) and (c). Typically, the maximum amount of each component is no more than 80% by weight of the total weight of components (a), (b) and (c).

In general, it is preferred that component (a) is present in at least 15% by weight of the total weight of components (a), (b) and (c). In general, it is preferred that the weight of component (a) is not more than 70% by weight of the total weight of components (a), (b) and (c).

Component (b) may be present in at least 15% to 15% by weight of the total weight of components (a), (b) and (c).

In general, it is preferred that the weight of component (b) is not more than 40% by weight of the total weight of components (a), (b) and (c).

Component (c) is generally present in an amount of at least 15 to 20% by weight of the total weight of components (a), (b) and (c). In general, it is preferred that the weight of component (c) does not exceed 50% by weight of the total weight of components (a), (b) and (c).

It will be appreciated that the relative amounts of components (a), (b) and (c) may vary, and the amounts used to obtain optimum properties may vary depending on the specific compounds used as components (a), (b) and (c) and rnyds. the individual system in which the composition is to be used.

In addition to components (a), (b) and (c), the composition may contain any other components. These other components may be liquids including water and organic liquids such as aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ketones, esters, ethers and alcohols. The components of the composition are typically solids, and when the component and (a), (b) and (c) are used with a liquid, they are either dissolved or dispersed in the liquid medium. Some components of the composition may be more soluble in a particular liquid medium than other solvents, and in such systems the composition may be partially dissolved and partially dispersed. However, it is generally preferred to use a liquid medium in which all components (a), (b) and (c) are soluble or in which all components (a), (b) and (c) remain substantially insoluble. If a liquid medium is present, the composition of components (a), (b) and (c) may be present in an amount of 1 to 99% by weight of the total composition of the liquid medium and the composition. Typically, the amount of composition is from 2 to 50% by weight of the total amount of liquid medium and composition.

The composition may also contain other antimicrobial agents such as antibacterial agents. Compounds which may be added to the composition as antibacterial agents include imidazolidinyl urea, 1,2-dibromo-2,4-dicyanobutane, 5-chloro-2-methyl-4-isothiazolin-3-one and its magnesium salts, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one and its salts, 2-bromo-2-nitropropane-1,3-diol, glutaraldehyde, polyhexamethylene-25-biguanide, triazine derivatives and oxazolidine and its derivatives. A beneficial effect is obtained if the composition contains 1,2-benzisothiazolin-3-one or a salt thereof.

The composition may alternatively or additionally contain one or more solid components which may act as carriers or diluents. Solids that can be used as a possible component include inorganic substances such as metal oxides or mixtures or compounds thereof, for example alumina, silicon dioxide, titanium dioxide, zinc oxide, talc, pyrophyllite, gypsum, lime, diatomaceous earth, bentonite and , and organic substances such as wheat flour, soybean meal, wood flour, pShkinan flour and lignin.

The solid is preferably in finely divided form, and typically has an average particle size of no more than 5 micrometers. The optional solid may be added to the composition in an amount of 1 to 95% by weight based on the total weight of the composition and any solid, and in general the possible solid may be present in an amount of 10% by weight and up to 80% by weight. -% of composition.

The composition may contain an antifouling agent, especially if the composition is in solid form. Suitable anti-fouling agents include dodecylbenzene, tridecyl-15-octadecanoate, trimethylolpropane tridodecenoate,

Twitchell 01jy, Ensitol USN and MineralOil.

If the composition contains a liquid in which the solid components of the composition are dispersed, the dispersion will contain a surfactant effective as a dispersant to maintain the solid components as a dispersion. Any surfactant that is an effective dispersant and is known to be suitable for use in biocidal compositions can be used, for example, alkylene oxide copolymers and alkylene oxide adducts of fatty alcohols, alkylphenols, and amines such as ethylenediamine. Other surfactants that can be used as dispersants include sodium lignosulfonate, E0 / PO / E0 block copolymers, ethylene oxide condensates with nonylphenol 30 or β-naphthylene-naphthenyleneaminolenylene condensates or PO0 / E0 copolymer condensates condensates of sulphonic acid and formaldehyde. The surfactant is typically present in an amount of 0.1 to 20% by weight of the total dispersion to which the surfactant is added. In addition to the surfactant, the dispersant contains mold components which are known to belong to the blossom composition, for example thickeners. Substances which may be used as thickeners include polysaccharide, xanthan gum, sodium magnesium silicate, heteropolysaccharide, alginates, carboxymethylcellulose, acacia, polyacrylic acid and polyvinyl alcohol.

Components (a), (b) and (c) of the composition of the present invention are generally clinical substances. Composition-10 black in combination with possible earth solids can be used as a solid mixture, very preferably as a powder mixture. A solid mixture of this type preferably consists of particles with an average particle size of at most 25 micrometers and in particular at most 10 micrometers. Components (a), (b) and (c) and other possible solids may be available as a powder of suitable particle size. All solids with a larger particle size than desired can be subjected to a particle size reduction step, for example, grinding using an impact mill, ball mill, or laboratory mill available from Christy and Norris. The components of the composition are subjected to a suitable mixing procedure for solids, for example, a drum mixer or a mixer using a powder mixer such as a Loedinge mixer or a Henschel mixer. Preferably, all substances having a large particle size are subjected to a particle size reduction before the solids mixing step is performed. However, it should be noted that, if desired, the solids can be mixed and the resulting mixture can then be subjected to particle size reduction, but this is generally a less unsatisfactory and inefficient procedure.

If the composition is mixed with a liquid medium 35 to form a dispersion, mixing with the liquid can be accomplished by suitable dispersing techniques using a colloid mill, a colloid mill, a high shear volume Silverson or Ultra-Turrax mixer, a bead mixer, a bead mixer. If a high-performance dispersing technique is used, it is able to cause a reduction in the particle size of the solids, and thus a pre-performed reduction in the particle size of the dry praise may be unnecessary. When preparing a dispersion in a liquid carrier, a solid mixture may be prepared initially and the mixture may be dispersed in the liquid in the presence of other additives such as surfactants, thickeners and the like. Alternatively, each solid component of the composition, including any possible solid components, may be dispersed in a liquid carrier that is the same for each solid, and then the resulting dispersions are combined. Yet another alternative is to dry mix some of the solid components, form a dispersion from the mixture, and mix this dispersion with one or more other solid components and an optional dispersion. Such a process may be advantageous if one or more solid components have a large particle size which is inevitable to be reduced, whereby such a particle size reduction is carried out using a high-efficiency dispersion process and the resulting dispersion is mixed with the other solid components.

As previously described, the composite of this invention is a mixture of biocides. Thus, the composition of this invention-30 nOn can be used as a biocide.

More specifically, the composition of the present invention has a particularly effective antifungal effect. Thus, the composition of the present invention can be used for the treatment of various agents to inhibit the growth of microorganisms, in particular fungi and algae.

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A further feature of the present invention is a method of inhibiting the growth of microorganisms in or on a medium comprising treating the medium with a composition comprising components (a), (b) 5 and (c) as defined above.

The composition can be used under conditions in which microorganisms, especially fungi and algae, grow and cause problems. Systems in which microorganisms cause problems include liquid systems, especially aqueous ones such as cooling aqueous solutions, metal fillers, geological drilling lubricants, polymer emulsions and coating compositions such as paints, alkyd paints and varnishes, and myds and solids such as wood solids. and synthetic polymers, especially those containing a significant proportion of additives. The composition can be preserved in such substances and is particularly useful when added to a paint, alkyd varnish or varnish to which it imparts antifungal and algae control properties. The composition is useful when added to a synthetic polymer weft polyvinyl chloride containing a plasticizer such as an ester, for example a phthalic acid or adipic acid diester, or an epoxidized oil.

The composition of the invention can be used in coating compositions to provide an additional effective amount. 25 An antimicrobial composition according to the invention.

The coating composition may be a paint, an alkyd varnish or a lacquer and in particular a paint, for example an emulsion paint. The amount of composition present in the coating composition is typically an amount sufficient to increase the total weight of the active ingredients, i.e. components (a), (b) and (c), to 0.001 to 50% by weight and in particular 0.1 to 50% by weight. 2% by weight of the total weight of the coating composition.

The composition imparts antifungal and anti-algae properties to the coating composition. However, many of the compounds used to impart antifungal properties contain iodine, and unlike such compounds, the compositions of this invention exhibit only a great change in the color of the paint film upon exposure to light. Thus, the compositions of this invention can be used under conditions in which many iodine-containing compounds would cause an undesirable color change in the paint film, while the compositions of this invention cause little or no color change.

The composition of the invention may also be used in the plasticized polymer composition to further provide an effective amount of the antimicrobial composition of the invention.

The polymer is typically plasticized PVC, which contains the plasticizer or plasticizers in an amount of 10 to 100% by weight of the polymer. The composition of this invention is preferably added to the polymer in an amount of 0.01 to 5% of the composition based on the amount of polymer.

We have found that while the compositions of this invention have particularly useful antifungal properties, other compositions comprising one or two of components (a), (b) and (c) together with other biocidal components are, in excess of being less effective as antifungal agents.

The following illustrative examples illustrate additional features of the invention. In the following tests and examples, all parts are by weight unless otherwise indicated.

The compositions obtained in the following examples were subjected to microbiological evaluation as paint film fungi-30 dressings. The anti-algal properties of the My6s compositions were tested. Microbiological testing was performed as follows:

The activity of the products against fungi was tested with one or more fungi Alternaria alternata, Au-reobasidum pullulans, Cladosporium Herbarum, Phoma vio-35 lacea and Stemphylium dendriticum.

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Evaluation as a paint film fungicide

The test compositions were obtained as described in Examples 1-6 and Comparative Examples. The compositions were added as a clinical mixture to outer acrylic-5 emulsion paint Sytteisiln (based on Revacryl 1A latex at pH 9) in glass bottles and mixed to give a final paint concentration of 1.0, 0.5 and 0.25% w / v.

Bottles 10 containing paint and biocide composition were sealed and stored at 40 ° C for three days.

For each paint, small wooden test pieces were prepared by priming and then brushing two intact flat coatings.

One set of corrugated test pieces was stolen from the thief-15 in an ambient lamp room, in the dark. The second set and baked test pieces were placed in a rinsing device where the test pieces were sprayed ve-Delia for one day, and the test pieces were removed from the rinsing device and dried. For one more set of test cap-20 pieces, rinsing was performed for two days.

The corrugated test pieces of that yoke were transferred to a room with high humidity. Each test piece was then inoculated by spraying a combined fungal suspension of Alternaria alternata, Aureobasidum pullulans, Clados-25 porium herbarum, Phoma violacea and Stemphylium dendriticum.

Incubation was performed at 25 ° C for four weeks.

The yoke of this episode was examined for fungal growth of paint films with the naked eye and an optical stereomicroscope.

30 Examples 1-6

A series of compositions of the present invention and a series of reference compositions were prepared by mixing two or more solid components together in a mortar or grinder using the ratios shown in Table 1.

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Table 1 provides further details of the resulting composition.

Table 1 g Example or Component (¾) (parts by weight)

worth juesim, i ^ c ptf 20 DS ^ ZpT BS pp yy p & TT

A 75 25 B 55 25 20 C 50 50 D 20 80 10 1 60 20 20 2 40 20 20 20 3 40 20 40 4 30 20 20 30 5 55 25 20 15 6 35 25 20 20 E 40 20 40 P 20 40 40 G 55 25 20 H 35 25 20 20 20 I 55 25 20 J 35 25 20 20 K 55 25 20 L 35 25 20 20 M 55 25 20 N 35 25 20 20 25

Explanations for Table 1 (a) NC is tetrachloro-isophthalonitrile.

DU is 3- (3,4-dichlorophenyl) -1,1-dimethylurea.

30 ZO is silicon oxide with a particle size of less than one micrometer.

DS is 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridyl.

AM is diiodomethyl-4-methylphenylsulfone.

35 ZPT is zinc-2-mercaptopyridine N-oxide.

17,92642 BS is a commercially available bloside containing 30% by weight of 2-thiocyanomethylthiobenzothiazole as the active ingredient, the remainder being an inert solvent.

PP is (RS) -2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexen-2-ol.

TY is a commercially available bloside containing 40% by weight of 3-iodo-2-propynyl N-n-butyl carbamate as active ingredient, the remainder being 10 inert.

DA is 3,4,5-trichloro-4- (propylsulfonyl) pyridine.

TT is tetrachloroterephthalonitrile.

Examples 7-24 The compositions of Examples 1 to 6 and Comparative Examples were evaluated as paint film fungicides using the method described earlier. For comparison, paints containing only tetrachloroisophthalonitrile (NC), 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DU), 2,3,5,6-tetrachloro- 4- (methylsulfonyl) pyridine (DS), diiodomethyl-4-methylphenylsulfone (AM) or zinc oxide (ZO). The results obtained are shown in Table 2.

Table 2 '25

Example or Composition Fungal Growth (d) (e) _ Comparative Example (ai (b) X lc) _UL_LI_L2 0 A 0.25 1.1 2.2 5.5 PA 0.5 1.1 3.5 1.3 30 QA 1.0 1.1 A, 4 2.3 RB 0.25 1.2 A, 5.5

S B 0.5 2.2 3, A 2, A

TB 1.0 0.2 1.2 A, 5 7 1 0.25 0.0 2.3 5.5 35 β 1 0f5 0.1 0.1 2.3 9 1 1.0 0.0 0.0 0.0 10 2 0.25 0.0 1.3 5.5 11 2 0.5 0.0 1.2 3.3

Table 2 (continued)

Example or Composition Fungal Growth (d) (e) Comparative Example. (>) (b) _Z (c) UL_kl_L2 18 92642 5 12 2 1,0 0,0 0,0 0,0 13 3 0,25 0,0 1,2 1,3 14 3 0,5 0,1 0.1 0.2 15 3 1.0 0.0 0.0 0.0 10 16 4 0.25 0.0 0.1 3.4 17 4 0.5 0.0 0.0 0.1 18 4 1.0 0.0 0.0 0.0 UC 0.25 1.3 HD 5.5 VC 0.5 1.1 HD 1.1 15 WC 1.0 0.1 HD 1.1 XD 0, 25 2.1 HD 4.5 YD 0.5 1.1 HD 3.3 ZD 1.0 0.1 HD 0.0 AA E 0.25 2.2 HD 5.5 AB. E 0.5 0.0 HD 4.3 20 AC E lf0 0.0 HD 5.5 AD * P 0.25 2.3 HD 5.5 AE P 0.5 1.3 HD 5.5 AP P 1 .0 1.1 HD 4.5 AG G 0.25 1.3 4.5 5.5 25 AH G 0.5 1.1 2.2 2.3 AI G 1.0 0.1 1.2 0.1 AJ H 0.25 0.3 5.5 3.4 AK H 0.5 1.1 3.4 4.4 AL H 1.0 1.1 1.2 0.0 30 AMS 1 0.25 1, 2 4.5 5.5 AH 1.0.5 0.0 4.5 5.5 AO I 1.0 0.1 1.3 4.5 AP J 0.25 3.5 2.5 5.5 AQ J 0.5 2.3 3.5 5.5 AR J lf0 0.1 2.3 5.5 35

Example or Copticum_ Fungal Growth (d) (e) _ Comparative Example (a, (b) χ fc) _jjl_y, _L2

Table 2 (continued) 19,92642 5,19 5 0.25 0.0 1.1 0.2 20 5 0.5 0.0 0.0 2.2 21 5 1.0 0.1 0.0 0.0 22 6 0.25 0.1 1.2 2.4 23 6 0.5 0.0 0.1 1.2 10 24 6 1.0 0.0 0.0 0.1 AS K 0.25 1.2 3 .5 4.4 AT K 0.5 1.1 4.5 4.4 AU K 1.0 0.1 4.4 2.3 AV L 0.25 2.3 3.5 1.3 15 AW L 0.5 1.3 3.5 0.1 AX L 1.0 0.1 2.2 1.1 AY M 0.25 1.2 5.5 5.5 AZ M 0.5 0.1 1 2 5.5 BA M 1.0 0.0 0.1 2.2 BB N 0.25 5.5 5.5 5.5 20 BC N 0.5 2.2 5.5 5.5 BD N 1 .0 0.0 1.1 5.5 BE NC 0.25 3.4 4.4 5.5 BF NC 0.5 2.3 4.5 3.5 BG NC 1.0 0.0 2.5 4.5 25 BH NIL NIL 5.5 5.5 5.5 BI DU 1.0 5.5 ND 5.5 BJ DS 0.25 2.2 ND 5.4 BK DS 0.5 1.1 ND 2 .3 BL DS 1.0 0.1 ND 1.0 30 BH AM 0.25 0.0 ND 4.4 BN AM 0.5 0.0 ND 1.2 BO AM 1.0 0.0 ND 0.0 BP ZO 1.0 5.5 ND 5.5 20 92642

Explanations for Table 2

(a) is as described in the explanations of Table 1

(b) Numbers and individual letters refer to the products of Examples 1 to 6 and Comparative Examples A to N.

(c)% is given as% m / v of the composition additive based on the mucilage.

(d) UL means a test piece that has not been rinsed.

10 LI means a test piece that has been rinsed for one day.

L2 means the test piece that has been rinsed for two days.

(e) 0 means no surface growth.

15 1 indicates less than 1% fungal growth on the surface.

2 indicates 1 to 10% fungal growth on the surface.

3 indicates 10-30% fungal growth on the surface.

4 indicates 30-70% fungal growth on the surface.

5 indicates more than 70% fungal growth on the surface.

It will be appreciated that, compared to reference compositions, the compositions of this invention have a significantly better antifungal effect both before and after rinsing.

Examples 25-28 Samples taken from the compositions of Examples 3-6 were tested for anti-algal activity. The experiment was performed using a bottle-shaking technique for a test day of 21 days at an incubation temperature of 21 ° C. The compositions were prepared at various concentrations in algae growth medium and exposed to a mixture of two algae, namely Trentepohlia Aurea and Nostoc commune. The results of the experiments are presented by table in Table 3.

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Table 3

Example Composition MIC (ppm)

(B) _ (JQ

25 3 25 5 26 4 12.5 27 5 12.5 28 6 6.25

The explanations in Table 3 10 (b) are defined in the explanation in Table 2.

f) The MIC is the minimum inhibitory content of the composition, expressed as ppm of the composition, based on the weight of the test substance.

According to the composition according to the invention, the following test method was evaluated as a fungicide in a PVC film using the following test method:

Evaluation as a fungicide in a PVC film The test compositions were obtained as described in Examples 3 to 4. The PVC pellets were placed in a bowl of 20 kitchen mixers, and the composition obtained as described in Example 3 or Example 4 was added, and then the contents were mixed for two minutes without heating. The bowl was then heated with hydrolyz, and then the other components used in the manufacture of PVC were slowly added, the other components and their proportions being as shown in the following "PVC Preparation Table". The resulting mixture was stirred until the sample became a fluffy dry powder.

i PVC preparation table 22 92642

Compo -___ Preparation (phr) __

nentti_ABCDEFGH

5 PVC 100 100 100 100 100 100 100 100 DOP 50 60 50 60 ESO 7 10 7 10 7 10 7 10

Phot 2 2 11 10 Ba2n 2 2 2 2 SA 0f5 0,5 0,5 0,5 0,5 0,5 0,5 0,5

CaZn 2 2 2 2 1178 0,5 0,5 0,5 0,5 DOA 50 60 50 60 15 -

Explanations for PVC Formulation Table PVC is a polymer available as PVC-2095 resin from Georgia Gulf Corp. Plaquemine, LA, 20 USA.

DOP is bis (2-ethylhexyl) phthalate ESO is epoxidized soybean oil.

Phos is an alkylaryl phosphite available from the Argus Division of Wit-co Corp., Brooklyn, NY, USA under the names LE98.

BaZn is a barium slabkkstablllator available from Witcon Argus Division under the name LZll.

SA is octadecanoic acid.

CaZn is a calcium zinc stabilizer available from Witcon Argus Division under the name LN138.

1178 is an additive available from Witcon Argus Division under the brand name 1178.

DOA is a bis (2-ethylhexyl) adipate.

23 92642

Each of the PVC products was formed into a film using a 19 mm (3/4 inch) Brabender extruder with a 10.2 cm (4 inch) wide die orifice of varying thickness. The extruder was operated at 5 speeds of 40 rpm using a lamp profile of 155 ° C, 170 ° C and 190 ° C. The extruded polymer was directed to a chill roll operating at 9 rpm. The thickness of the obtained film was 8-12 micrometers. The film was cut into 3.81 cm (1.5 inch) ne-10 lids, which were evenly placed on top of the front salt poured base salt medium containing 2% agar and a larger proportion (10% of the final medium) of plasticizer that was either bis ( 2-ethylhexyl) phthalate, bis (2-ethylhexyl) adipate or epoxidized soybean oil.

Cultures were incubated at 30 ° C and 96% humidity. Plates containing the membrane were incubated for 7-10 days at 30 ° C and 96% humidity, and its yeast was checked for fungal growth.

Examples 29-52 The compositions of Examples 3 and 4 were evaluated as PVC film fungicides using the method previously described. For comparison, a PVC film that did not contain added fungicide was evaluated under the same conditions. One fungus was used in each test. The results obtained 25 are shown in Table 4.

Example or Composition Comparative Example of PVC Fungus Growth (^

Table 4 24 92642

_ <b) I (hl (1) _m_PC

5 BQ NIL NIL A a / b f BR NIL NIL B c f BS NIL NIL C ae BT NIL NIL D 0 f BU NIL NIL E O e 10 BV NIL NIL F O e BW NIL NIL 6 af BX NIL NIL H O e _

29 3 0.5 A O O

30 3 0.5 B O 0

15 31 3 0.5 C O O

32 3 0.5 D 0 0

33 3 0.5 E O O

34 3 0.5 F O O

35 3 0.5 G O O

36 3 0.5 H O O

20 37 3 0.15 A O O

38 3 0.15 B O O

39 3 0.15 C O O

40 3 0.15 D O O

41 3 0.15 E 0 O

25 42 3 0.15 F O O

43 3 0.15 G O O

44 3 0.15 H 0 0

45 4 0.15 A O O

46 4 0.15 B O 0

30 47 4 0.15 C O O

48 4 0.15 D O O

49 4 0.15 E O O

50 4 0.15 F O O

51 4 0.15 G O O

52 4 0.15 H O O

35 25 92642

The explanations in Table 4 (b) are defined in the explanations in Table 2.

(h)% is given as% m / v composition based on the PVC content of the preparation.

5 (i) A to H are the preparations shown in the PVC formulation table.

(j) AN is Aspergillus niger PC is Penicillium citrenum 0 means no growth was observed 10 a means that very waxy growth was observed b means small clumps were observed c means large clusters were observed d means that growth was observed in three si -15 wool e means that growth was observed on all sides f means wipes the surface of the film was completely covered 20

In the tests presented by Edelia, the films were Samei. However, films containing compositions of 0.75%, 1.0% or 2.0% were lapable.

Claims (10)

92642 An antimicrobial co-rot, characterized in that it contains (a) at least one halogenated aromatic 1,2-tal 1,3-dinitrile, (b) at least one substituted urea and (c) at least one halogenated aromatic an alkyl sulfoxide or sulfone in which, when the aromatic group is the only halogen-containing group, it contains at least four halogen substituents. 2. The composition of claim 1, comprising the following: dinitrile in the form of: 15 Xn_ ”vari varje X, vilka kan var lika eller olika, ar en 20 halogenatom, n ar från et till fyra och nitrilgrupperna ar antingen i 1,2- eller 1,3-stail-Ning i fOrhållande till varandra. Composition according to Claim 1, characterized in that the dinitrile has the formula: '-6- in which each X, which may be the same or different, is a halogen atom, n is from one to four and the nitrile groups are either 1,2 or 1.3 position in relation to each other. • | Composition according to Claim 1 or 2, characterized in that the substituted urea has the formula: 0 R1 30. C 1-1 R 2 wherein Ar is aryl, substituted aryl, heteroaryl-35, substituted heteroaryl, heterocyclic or substituted heterocyclic, • 92642 R 1 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, , alkynyl, substituted alkynyl, cycloalkyl, substituted cycloalkyl, alkoxy or substituted alkoxy, and R 2 is a hydrogen atom or a group defined for R x. 3. A composition according to claims 1 or 2, wherein n-25 are optionally substituted by urea having the formula: At <\ o ^ r1 - C - 30 vari Ar ar en aryl-, substituted aryl-, heteroaryl-, substituted heteroaryl -, heterocyclic or substituent 35 heterocyclic group, 92642 R1 Sr en alkyl, substituent alkyl, alkenyl, substituent alkenyl, alkynyl, substituent alkynyl, cycloalkyl, substituent cycloalkyl, alkoxy or substituent alkoxy Science A composition according to claim 3, which is substituted by a group having the substituent or a substituent or a substituent, wherein a halogen atom or a halogen alkyl group, R 1 and R 2 are selected from the group consisting of methyl or methoxy, or the substituent R1 and R2 are annan an vate. Composition according to Claim 3, characterized in that the group Ar is unsubstituted or contains one or two substituents which are halogen atoms or lower alkyl groups, R 1 and R 2 represent hydrogen, methyl or methoxy, wherein at least one of the substituents R 1 and R 2 is other than hydrogen. 5. A composition according to claims 1-4, comprising a solvent and a halogenated aromatic alkylsulfoxide or a sulfonic acid. Black: Ar1SOxR3 vari Ar1 is an aryl, aryl, heteroaryl, heteroaryl, heteroaryl, heterocyclic or substituted heterocyclic group, R3 is an alkyl or an alkyl group, an aryl or an alkyl group having an Ar1 or R3 group the halide is a halogen substituent and, where R3 is a halogen, the halogen Ar1 is a halogen substituent. 5 R2 is en or a group R1 is defined. Composition according to any one of Claims 1 to 4, characterized in that the at least one halogen-containing aromatic alkyl sulphoxide or sulphone has the formula: Ar1 is aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocyclic or substituted heterocyclic, R3 is alkyl or substituted alkyl, x is one or two and at least one of Ar1 and R3 contains at least one halogen substituent and, if R 3 does not contain halogen, then Ar 1 contains at least four halogen substituents. 6. A composition according to claim 5, wherein Ar1 is an pyridine ring having a halogen substituent and R3 is an unsubstituted alkyl group having 1 to 12 cholatom or an Ar1 substituent having an aryl group, R3 or a halogen-substituted alkyl group. 92642 A composition according to claims 5, characterized in that Ar 1 is a pyridine ring having four and halogen substituents and R 3 is an unsubstituted alkyl group having 1 to 12 carbon atoms, or Ar 1 contains an aryl group, R 3 is a halogen-substituted methyl group and x is two. 92642 A composition according to claim 1, wherein (a) or tetrachloroisophthalonitrile, (b) Sr 3- (3,4-dichlorophenyl) -1,1-dimethylurea and (c) 2.3; 5,6-Tetrachloro-4- (methylsulfonyl) pyridine or diiodo-5-methyl-4-methylphenylsulfone. Composite according to claim 1, characterized in that (a) is tetrachloroisophthalonitrile, (b) is 3- (3,4-dichlorophenyl) -1,1-dimethylurea and (c) is 2,3,5 , 6-tetrachloro-4- (methylsulfonyl) pyridine or diiodomethyl-4-methylphenylsulfone. 8. A composition according to claims 1-7, further comprising 10% by weight of a component and a component of component (a), (b) and (c) of total components of component (a), ( b) and (c). Composition according to any one of Claims 1 to 7, characterized in that it contains at least 10% by weight of components (a), (b) and (c) of each component (a), (b) and (c). ) of the total weight. 9. A composition according to claims 1-8, further comprising a method of preparing an amine stone as an active ingredient, a solid and an amylic acid having the same effect as the talc of talc: pyrite, zinc dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, gypsum, lime, kiselgur, bentonite, skumlera, vetemjOl, soyamjOl, tråmjOl, nOtskalsmjOl eller lignin. Composition according to any one of Claims 1 to 8, characterized in that it contains at least one additional component which is a solid additional component which is at least one of the following: alumina, silica, titanium dioxide, zinc oxide, talc, pyrophyllite, gypsum, lime, diatomaceous earth, bentonite, effervescent clay, wheat flour, soya flour, wood flour, nutshell flour or lignin. A method for inhibiting the growth of microorganisms in or on a substrate, characterized in that the silicone is treated with a composition according to any one of claims 1 to 9. 92642 * 1. An antimicrobial composition comprising a mixture of (a) acetone 5 and halogenated aromatic 1,2- or 1,3-dinitrile, (b) acetone and substituents urea and (c) acetone and halogenated aromatics alkylsulfoxide or sulfone, in which case the alkylstone is a halogen substituent, having an aromatic group or a halogen halogen group. 10. For use in the preparation of microorganisms in a medium or medium, as described above, the composition of the composition according to patent invention 1-9.